Electrophotographic material

ABSTRACT

A chlorine-containing product is obtained by reacting N-(b -hydroxypropyl)-carbazole with thionyl chloride.ALSO:A polymeric photoconductive composition contains a polymeric reaction product as below, with or without the various additives mentioned in Specification 964,875, i.e. sensitisers, plasticizers, pigments, and agents controlling viscosity, free flow, ageing, oxidation, thermal stability and gloss; the polymeric products are those made by reacting (a) a polymer with a halogen-containing aromatic or heterocyclic compound, (b) a halogen-containing polymer with an aromatic or heterocyclic compound, or (c) a polymer and an aromatic or heterocyclic compound with a di- or poly-halogen compound. Details are given of the reactions of (a) polystyrene with N-(b -chloropropyl)-carbazole, and (b) polyvinyl chloride with fluorene, naphthalene and toluene. Other specified reactants are: chlorinated polyvinyl chloride, polyvinylbenzyl bromide, polyisophenylbenzyl bromide and a copolymer of vinyl chloride and styrene; anthracene, carbazole, phenthiazine, phenoxathiine, acridine, lophine and derivatives thereof. The di-halogen compound for method (c) may be a methylene halide, ethylene dibromide or chloroacetyl chloride. A Friedel-Crafts catalyst is used for each reaction. Suitable solvents for casting the products on to a support are methylene chloride, chloroform, carbon tetrachloride, dimethylformamide, acetone, benzene, tetrahydrofuran and mixtures thereof. Other synthetic resins may be present in the compositions, e.g. polyvinylcarbazole and a terpolymer of vinyl chloride, vinyl acetate and maleic anhydride. In particular, the polymeric photoconductors of Specifications 964,871, 964,875 and 964,877 may be present. Specification 964,778 also is referred to.  The Provisional Specification states that the substances mentioned in Specifications 883,787, 883,788, 964,873, 964,874 and 964,872 may also be present.

ted states 3,122,435 ELECTRGPHDTOGRAPHIC MATERIAL Robert Joseph Noe, Berchem-Antwerp, and Renaat Frans Heylen, Deurne-Antwer Belgium, assignors to Gevaert Photo-Producten N.V., Mortsel, Belgium, 21

Belgian company No Drawing. Filed Apr. 21, 1961, Ser. No. 104,504 Claims priority, appiicafion Belgium Apr. 22, 196i) 9 Claims. ((31. %l)

Q1 Q2 l i l I CHR f rms wherein A represents a single bond, or a divalent organic radical,

R and R each represents a hydrogen atom or a lower alkyl radical,

Z represents a sulphur atom or a single bond,

Z represents a methine group or a nitrogen atom,

Q and Q together represent the atoms necessary to complete an aromatic nucleus, and

Q and Q together represent the atoms necessary to complete an aromatic nucleus.

According to said patent application a series of suitable compounds which cause an increase of the sensitivity in the ultra-violet and visible Wave range of the spectrum may also be incorporated in the photoconductive layers irrespective of whether or not they themselves possess photoconductive properties.

Now has been found that the general sensitivity in the ultra-violet and visible wave range of the spectrum and/ or the sensitivity to electromagnetic rays of a particular wave range of the visible spectrum of the photoconductive layer of an electrophotographic material as described in said patent application, may also be increased by incorporating in this photoconductive layer in combination with a 1,2,3- triazole compound according to the following general Formulae I and II, a triarylmethane dyestulf with ring closure according to the general Formulae Ill and IV.

R R R R R and R each represents a member selected from the group consisting of a hydrogen atom,

3,122,435 Patented Feb. 25, 1964 an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an amino group, a substituted amino group, a carboxyl group, a substituted carhoxyl group, a hydroxyl group, a substituted hydroxyl group, a mercapto group and a substituted mercapto group, the grouping R and R together, and the grouping R and R together each represent the atoms necessary to complete a ring system of the class consisting of a carbocyclic nucleus, a substituted carbocyclic nucleus, at system of fused carbocyclic nuclei, a system of substituted fused carbocyclic nuclei, a heterocyclic nucleus, a substituted heterocyclic nucleus, a system of fused heterocyclic nuclei, and a system of substituted fused heterocyclic nuclei.

H wherein: R;, R and R' each represents a member selected from the group consisting of a hydrogen atom and an alkyl radical, such as an ethyl radical,

M and M each represents a member selected from the group consisting of a hydrogen atom and an alkali metal atom,

X and Z each represent a member selected from the group consisting of a hydrogen atom, a bromine atom, an iodine atom, and a hydroxyl group,

X and Z each represents a member selected from the group consisting of a hydrogen atom, a bromine atom and an iodine atom,

Y Y Y and Y each represents a member selected from the group consisting of a hydrogen atom and a chlorine atom.

The 1,2,3-triazole compounds preferably are used in an amount ranging from 0.1 to 5% based on the weight of the polymeric compound of the photoconductive layer, and the triaryl methane dyestuffs preferably are used in an amount ranging from 0.01 to 1% based on the weight of the polymeric compound of the photoconductive layer.

The compounds corresponding to the above mentioned Formulae I and II, which appeared from the experiments to give in combination with triaryl methane dyestuffs according to the general Formulae III and IV particularly good results when used for the preparation of the electrophotographic material according to the present invention, are identified hereinafter in Tables I and II.

TABLE II 1,2,3-Triazoles According to the General Formula 11 Compound R4 Br I Re 5 H COOC H CH 6 NHCuH5 COOCZH5 CH3 7 1 lH-O ONH:.- 00002115" CH3 8. a

9 H NO 1O CH3 12 CH3 O N- 13 H i g As such compounds corresponding to one of the above mentioned Formulae III and IV which give in combination with the 1,2,3-triazole compounds according to the general Formulae I and 11 very good sensitizing effects when incorporated in the photoconductive layer of the electrophotographic material according to the present invention can be mentioned- According to Formula III:

Rhodamine G extra (CI. 45150) Rhodamine B (CI. 45170) Rouge Fanal 6 B Supra pate and Rouge Fanal Supra poudre (both CI. 45175) According to Formula IV:

Erythrosine Blaulich (CI. 45430) Rose Bengale N, Rose Bengale Double cone. and

Rose Bengale (all CI. 45440) Gallein MS. (CI. 45445) Phloxin BBN (CI. 45410 A) Erythrosine (CI. 45430) Fluoreszein Natrium (CI. 45350) Further details according to the preparation of an electrophotographic material, the addition of other photoconductive compounds and sensitizers, as well as the incorporation in the photoconductive layer of additives well known in the technique of coating such as plasticizers and pigments, the choice of the support and the techniques used on applying the photoconductive layers to the support are known to those skilled in the art and can also be taken from our US. patent application Ser. No. 11,129, filed February 26, 1960. Regarding the use of the obtained photographic material, the electrostatic charging of this photographic material, the formation and the development of the latent image, the transfer (if any) of the image to another support and the methods for fixing the developed image, it may also be referred to the particulars stated in our said US. patent application Ser. No. 11,129, filed February 26, 1960.

The following examples illustrate the invention without limiting, however, the scope thereof.

EXAMPLE 1 On a baryta coated photographic paper of g./sq.m. is applied a layer from a solution consisting of Copoly(N-vinylcarbazole/methylacrylate) (46.6/53.4) g 10 Methylene chloride cm. Rhodamine B (CI. 45170) mg 40 Compound 8 of Table II mg 100 After drying the thickness of the layer amounts to 7 m. The electrophotographic material thus obtained is negatively charged with a corona device and next a positive microfilm image is projected on the light-sensitive layer. A linear enlargement of 4 times requires an exposure time of 30 see. with a 75 watt lamp. The latent image formed is developed by dusting with a mixture of the following.

Rouge Fanal 6 B Supra poudre (CI. 45175) Rose Bengale Double conc. (CI. 45440) Crystal Violet (C.I. 42555) EXATMPLE 2 To a baryta coated photographic paper of 90 g./sq.m. is applied a layer from the following solution:

After drying the thickness of the layer amounts to 8a. The photographic material thus obtained is negatively charged with a corona device and next the light sensitive layer is exposed for 2 sec. through a transparent original with a 100 watt lamp placed at a distance of cm. The latent image formed is developed and fixed as in Example 1. The final image is a strong copy of the original.

Similar results are obtained with the dyestulfs:

Vert diamant GX (CI. 42040) Blue Zapon Solide 3 G (CI. 51005) Turchese segnale luce NB (CI. 74160) Indulin Scarlet (C.I. 50080) EXAMPLES 39 Similar results as in Example 2 are obtained by substituting the following sensitizers for the compound 4 of Table I:

What We claim is:

1. An electrophotographic material comprising a photocond-uctive layer consisting essentially of a polymeric compound containing recurring units having the general formula wherein A represents a member selected irom the group consisting of a single bond and a divalent organic radical; R and R each represents a member selected from the group consisting of a hydrogen atom and a lower alkyl radical, Z represents a member selected from the group consisting of a sulphur atom and a single bond, Z represents a member selected from the group consisting of a methine group and a nitrogen atom, Q and Q together represent the atoms necessary to complete an aromatic nucleus, and Q and Q together represent the atoms necessary to complete an aromatic nucleus, and containing 0.01 to 1% based on the weight of said polymeric compound of a dyestuff of the group consisting of an oxazine dyestuff, a diazine dyestuff, a phthalocyanine dyestuif and a triarylearbenium salt which is of the group consisting of a triarylmethane dyestufi and a phthalein dyestuff and 0.1 to 5% based on the weight of said polymeric compound of a 1,2,3-triazo-le compound having a formula selected from the group consisting of:

8 wherein R represents a member selected from the group consisting of alkyl and an aryl radical;

R represents a member selected from the group consisting of alkyl and aryl;

R represents a member selected from the group consisting of alkyl and aryl;

'R represents (the member selected from the group consisting of hydrogen, alkyl, aryl, alkyl-substituted amino, and an ureido group;

R represents a member selected from the group consisting of alkyl, aryl and a carbalkoxy radical;

R represents a member selected from the group consisting of alkyl and aryl, and

X" represents the atoms necessary to complete an aromatic ring system.

2. An electrophotographic material comprising a photoconductive layer consisting essentially of a polymeric compound containing recurring units having tthe general formula wherein A represents a member selected from the group consisting of a single bond and a divalent organic radical, R and R each represents a member selected tfirom the group consisting of a hydrogen atom and a lower alkyl radical, Z represents a member selected from the group consisting of a sulphur atom and a single bond, Z represents a member selected from the group consisting of a methine group and a nitrogen atom, Q and Q together represent the atoms necessary to complete an aromatic nucleus, and Q and Q together represent the atoms necessary to complete an aromatic nucleus, and containing (a) 0.01 to 1% based on the Weight of said polymeric compound of a triarylmethane dyestuff with ring closure having a formula selected from the group wherein:

R' R and R' each represents a member selected from the group consisting of a hydrogen atom and an alkyl radical,

and

Yr fi-OM wherein M and M each represents a member selected from the group consisting of a hydrogen atom and an alkali metal atom;

X and Z each represents a member selected from the group consisting of a hydrogen atom, a bromine atom, an iodine atom, and a hydroxyl group,

. X and Z1 each represents a member selected from the group consisting of a hydrogen atom, a bromine atom and an iodine atom,

Y Y Y and Y each represents a member selected from the group consisting of a hydrogen atom and a chlorine atom;

and (b) 0.1 to 5% based on the weight of said polymeric compound of a l,2,3-triazole compound having a formula selected from the group consisting of: I

wherein:

R represents a member selected from the group consisting of aryl and an aryl radical;

R represents a member selected from the group consisting of alkyl and aryl;

R represents a member selected from the group consisting of alkyl and aryl;

R represents the member selected firom the group consisting of hydrogen, alkyl, aryl, alkyl-substituted amino, and an ureido group;

R represents a member selected from the group consisting of alkyl, aryl and a carbalkoxy radical;

R represents a member selected from the group consisting of alkyl and aryl, and

X represents the atoms necessary to complete an arcrnatic ring.

3. The material of claim 1 wherein said dyestuff is a triarylcarbenium salt with ring closure by an oxygen atom.

4. The material of claim 1 wherein said photo-conductive layer is in intimate contact with a conductive backing member.

5. The material of claim 2 wherein said photo-conductive layer is in intimate contact with a conductive backing member.

:6. -A photographic reproduction process which comprises electros-tatically charging the electrophotographic material of claim 1 and exposing said material to a light image, whereby a pattern of electrostatic charges according to said light image is created in said material, and developing a visible image of said light image by means of said pat-tern of electrostatic charges.

7. A photographic reproduction process which comprises electrostatically charging the electrophotographic material of claim 2 and exposing said material to a light image, whereby a pattern of electrostatic charges according to said light image is created in said material, and developing a visible image of said light image by means of said pattern of electrostatic charges.

8. A photographic reproduction process which comprises electrostatically charging the electrophotographic material of claim 4 and exposing said material to a light image, whereby a pattern of electrostatic charges according to said light image is created in said material, and developing a visible image of said light image by means of said pattern of electrostatic charges.

9. A photographic reproduction process which comprises electrostatically charging the electrophotographic material of claim 5 and exposing said material to a light image, whereby a pattern of electrostatic charges according to said light image is created in said material, and developing a visible image of said light image by means of said pattern of electrostatic charges.

References Cited in the file of this patent UNITED STATES PATENTS 3,037,861 Hoegl et al. June 5, 1962 

1. AN ELECTROPHOTOGRAPHIC MATERIAL COMPRISING A PHOTOCONDUCTIVE LAYER CONSISTING ESSENTIALLY OF A POLYMERIC COMPOUND CONTAINING RECURRING UNITS HAVING THE GENERAL FORMULA 